CN116177989A - High-strength zirconium silicate composite ceramic grinding medium and preparation method thereof - Google Patents
High-strength zirconium silicate composite ceramic grinding medium and preparation method thereof Download PDFInfo
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- CN116177989A CN116177989A CN202211724793.2A CN202211724793A CN116177989A CN 116177989 A CN116177989 A CN 116177989A CN 202211724793 A CN202211724793 A CN 202211724793A CN 116177989 A CN116177989 A CN 116177989A
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- zirconium silicate
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- zirconium
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- 238000000227 grinding Methods 0.000 title claims abstract description 227
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 title claims abstract description 193
- 239000000919 ceramic Substances 0.000 title claims abstract description 170
- 239000002131 composite material Substances 0.000 title claims abstract description 143
- 238000002360 preparation method Methods 0.000 title abstract description 31
- 239000002699 waste material Substances 0.000 claims abstract description 81
- 239000000463 material Substances 0.000 claims abstract description 78
- DNXNYEBMOSARMM-UHFFFAOYSA-N alumane;zirconium Chemical compound [AlH3].[Zr] DNXNYEBMOSARMM-UHFFFAOYSA-N 0.000 claims abstract description 64
- 239000000843 powder Substances 0.000 claims abstract description 62
- 239000004576 sand Substances 0.000 claims abstract description 58
- 229910052845 zircon Inorganic materials 0.000 claims abstract description 47
- 239000002270 dispersing agent Substances 0.000 claims abstract description 35
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910001570 bauxite Inorganic materials 0.000 claims abstract description 22
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 claims abstract description 18
- 229910000514 dolomite Inorganic materials 0.000 claims abstract description 18
- 239000010459 dolomite Substances 0.000 claims abstract description 18
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims description 62
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 6
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- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 6
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 57
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 34
- 239000012071 phase Substances 0.000 description 29
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 22
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
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- 239000004372 Polyvinyl alcohol Substances 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 230000009471 action Effects 0.000 description 4
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- 150000001875 compounds Chemical class 0.000 description 4
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- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 description 4
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- 229910001928 zirconium oxide Inorganic materials 0.000 description 4
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 3
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- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 3
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
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- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
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- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 2
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
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- 229910052710 silicon Inorganic materials 0.000 description 2
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- UVGLBOPDEUYYCS-UHFFFAOYSA-N silicon zirconium Chemical compound [Si].[Zr] UVGLBOPDEUYYCS-UHFFFAOYSA-N 0.000 description 2
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- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 241000695274 Processa Species 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
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- GNKHOVDJZALMGA-UHFFFAOYSA-N [Y].[Zr] Chemical compound [Y].[Zr] GNKHOVDJZALMGA-UHFFFAOYSA-N 0.000 description 1
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- 239000003513 alkali Substances 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical group O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
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- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention relates to the technical field of ceramic grinding media, and discloses a high-strength zirconium silicate composite ceramic grinding media and a preparation method thereof, wherein the high-strength zirconium silicate composite ceramic grinding media comprises the following components in parts by weight: 60-80 parts of low-grade tailing zircon sand, 15-30 parts of treated zirconium-aluminum composite ceramic waste grinding material powder, 0-10 parts of bauxite, 2-8 parts of dolomite, 1-3 parts of barium carbonate, 2-5 parts of yttrium oxide, 2-5 parts of sodium montmorillonite and 1-2 parts of dispersing agent. The raw material cost is low, the preparation method is simple, the prepared high-strength zirconium silicate composite ceramic grinding medium has high strength, high toughness, high wear resistance, high flushing resistance, high corrosion resistance and high wear resistance, and the abrasion is superior to that of the conventional zirconium silicate beads; the service life is longer than that of the conventional zirconium silicate beads, the cost is greatly reduced compared with that of the conventional zirconium silicate beads, and a green regeneration way is provided for the zirconium-aluminum composite ceramic waste grinding material.
Description
Technical Field
The invention relates to the technical field of ceramic grinding media, in particular to a high-strength zirconium silicate composite ceramic grinding media and a preparation method thereof.
Background
The superfine grinding sand mill is widely used in the fields of new energy battery materials, paint, coating and the like, and the materials are crushed through various complex motions such as mutual collision, extrusion and the like of grinding media; grinding media, also known as milling media, are critical to pulverizing materials. Currently, the grinding media are generally steel balls, glass beads, common ceramic beads, alumina beads, zirconium silicate beads, zirconium oxide beads and the like, and have various performances and different prices. The steel balls are poor in corrosion resistance and wear resistance, so that the application is less; the glass beads have low strength and high abrasion and are easy to pollute materials; the common ceramic grinding medium (the main crystal phase is aluminosilicate and glass phase), the product has coarse grains and poor performance, and can only be used in the low-end field; the alumina ceramic grinding medium (the main crystal phase is alpha alumina) is mainly applied to grinding of hard mineral materials, but the alumina material has low fracture toughness and poor wear resistance, and is not suitable for a high-speed sand mill; the zirconia has high specific gravity and good performance, belongs to high-end grinding materials, has very high price which is 3-4 times that of zirconium silicate beads, and limits the use of partial medium-high temperature working conditions due to phase change aging.
The zirconium silicate beads consist of uniform and dense zirconium silicate grains, the grain boundaries usually having a low melting point SiO 2 The content of zirconia in the glass phase is generally 45-65 wt percent, and the glass phase has good mechanical property and is an excellent grinding medium material. Is suitable for dispersing and grinding materials with higher viscosity, medium and high temperature and medium hardness, such as titanium dioxide, calcium carbonate, kaolin, paint and the like. The zirconium silicate beads are produced by a process which is basically high-temperature meltingThe zirconium silicate beads of the melting method are formed in a high-temperature melting state, so that the method has the defects of high energy consumption and environmental protection; and the size of the beads is difficult to be large, and is generally less than 2mm, so that hollows and tail beads are easy to form, broken beads can be formed under high-speed stirring in equipment, and the production is deadly influenced. At present, most of domestic manufacturers adopt a sintering method; foreign technology such as NanorZr-64 refractory zirconium silicate beads is also a high temperature sintering technology after titration molding in electrolyte.
The zirconium silicate grinding beads in the current market are various in variety, relatively chaotic and low in cost performance of part of products; some properties can not meet the use requirements, and the density is 3.8-4.0g/cm 3 The abrasion is larger and the compressive strength is lower. The main raw materials for producing the domestic zirconium silicate beads are ZrO 2 The high-quality zircon sand with the content of more than 66 weight percent is mostly produced in Australia, such as patent application number CN201610527894.9, which refers to a zirconium silicate ceramic grinding medium and a preparation method thereof, and the high-quality Australian sand is used as a raw material, so that the cost is high. There is little mention of the use of beneficiated ZrO 2 The low grade ore sand with the content of less than 60 weight percent is used for producing zirconium silicate beads.
The invention patent No. CN99118965.5, silicon zirconium ball manufacturing technology, discloses a method for preparing fused zirconite and cosolvent mixed fused microspheres, which has the defects of small size and poor particle size uniformity of zirconium silicate balls.
The invention patent with application number of CN201010122895.8 discloses a method for producing zirconium silicate balls by adopting isostatic compaction and high-temperature sintering technology, which has the defects of low isostatic pressing capacity and high cost, and can hardly produce beads with the diameter of less than 3mm, and the demand of the domestic market for microbeads with the diameter of less than 1mm is the dominant direction in the future along with wider and wider pulverizing and superfine demands.
The invention patent with publication number of CN103664152B, namely wear-resistant zirconium silicate medium ball and a preparation method thereof, is to prepare the zirconium silicate medium ball by a method of firstly spraying granulation to prepare seed balls and then rolling sintering. The patent describes that "can be used for the production of wear-resistant zirconium silicate medium spheres having a particle size of 0.5-10.0 mm", indicates the particle size range of the final product produced by the preparation method, because the inner core cannot be densified by using the granulating seed sphere, the method cannot be used for zirconium silicate medium spheres having a particle size of less than 0.5mm, and larger cores can appear on the beads above 0.5mm, resulting in low bead strength.
In the prior art, the recovery mode of waste zirconia such as zirconia-based composite ceramic grinding materials mainly comprises alkali fusion acidification, electric fusion purification, crushing, acid washing, calcining, sintering and other processes for extracting zirconium-containing and yttrium-containing compounds. The electric smelting purification process for recovering zirconia has high cost and low recovery efficiency. The invention patent with publication number CN108059186A (method for preparing zirconia powder by using solid waste zirconium as raw material and hydrothermal method) and the invention patent with publication number CN105036739A (method for preparing zirconium yttrium and zirconium aluminum composite powder by using yttrium stabilized zirconia solid waste) use acid-base process for recovery, which not only have complex process and high cost, but also cause new environmental pollution. The invention patent with publication number of CN102531588A discloses a method for preparing zirconia ceramics by recycling zirconia ceramic grinding waste, which adopts the processes of acid washing, impurity removal, calcination, crushing, forming and sintering to recycle the zirconia ceramic grinding waste, and has the defects of difficult treatment of waste acid and waste residue, secondary environmental pollution, and limited application of the produced zirconia ceramics due to poor sintering performance and high impurity content.
To sum up: the zirconium silicate ceramic grinding medium (zirconium silicate bead) is widely applied to industries such as paint, coating, titanium pigment and the like as a grinding medium with excellent cost performance, and the use amount at home and abroad exceeds 10000 tons/year, so that the zirconium silicate ceramic grinding medium is an excellent grinding medium. But there are the following places to be lifted:
(1) Compared with the zirconia ceramic material and the zirconium aluminum composite ceramic material, the zirconium silicate ceramic material has lower overall strength, and the linear speed reaches more than 20 m/s as the rotating speed of the sand mill is quite high, the impact force is quite large, and the strength requirement on grinding beads is quite high
To ensure high strength and low wear of the product; as a result, zrO is used for the most part in the current commercial products 2 The Australian sand with the content of more than 66 weight percent has low impurity content, but the cost for preparing the zirconium silicate beads is relatively high, and the problem of ore source exhaustion is also faced in the future.
(2) In the future, along with the exhaustion of zircon sand ore sources, how to efficiently recycle composite zirconium ceramic waste, other waste zirconium sources and the like in an environment-friendly way gradually becomes a problem which needs to be faced.
(3) Roll forming has been widely used in the preparation of ceramic grinding media having a size of 0.2mm to 20 mm. The technology has the advantages of simple equipment and production process and high production efficiency, and is a process suitable for mass production. In the rolling forming process, the ball blank is mutually rolled and extruded under the wetting action of the formula water by the repeated circulation of water spraying, rolling, powder adding and rolling, and the powder is adhered to the blank cores layer by layer to gradually grow up to form a target ball blank. The mode of combining the intermittent ball blank and the dry powder has great requirements on the bonding force between powder layers, and often has the defects of poor density, layering, cracks and the like of the ball blank, and the layering is more and more serious along with the growth of the ball blank (more than or equal to 3 mm), so that the ball blank is one of the main reasons of low grinding medium strength and great abrasion of ceramics, and the exertion of material performance is greatly limited. In the industry, adhesives such as PVA (polyvinyl alcohol) and CMC (sodium carboxymethyl cellulose) are often simply added into the rolling forming formula water to improve the forming performance, but because the bonding time in the production process is very short, organic components are difficult to sufficiently wet the surface of powder to achieve interlayer firm bonding, and sometimes layering is accelerated due to insufficient wetting (the wetting speed is lower than that of pure water) of the adhesives, so that the effect is not ideal.
(4) The low-grade tailing zircon sand raw ore brings various impurities and free quartz into the raw ore, so that the sintered glass phase has a great influence on the strength and toughness of the material, and the wear resistance is influenced; the conventional zirconium silicate grinding medium sintering process has little attention paid to the study of the toughening treatment of the sintered glass phase.
Therefore, there is a need for a high strength zirconium silicate composite ceramic grinding medium and a method for preparing the same to solve the above technical problems.
Disclosure of Invention
The invention aims to overcome the defects and provide a high-strength zirconium silicate composite ceramic grinding medium and a preparation method thereof.
In order to achieve the above purpose, the invention is implemented according to the following technical scheme:
the high-strength zirconium silicate composite ceramic grinding medium comprises the following components in parts by weight: 60-80 parts of low-grade tailing zircon sand, 15-30 parts of treated zirconium-aluminum composite ceramic waste grinding material powder, 0-10 parts of bauxite, 2-8 parts of dolomite, 1-3 parts of barium carbonate, 2-5 parts of yttrium oxide, 2-5 parts of sodium montmorillonite and 1-2 parts of dispersing agent.
Preferably, zrO in the low-grade tailing zircon sand 2 The content of (C) is 57-60wt%.
Specifically, zrO in Oriental zirconium mineral processing farm can be used 2 57-60wt% of low-grade tailing zircon sand.
Preferably, the treated zirconium-aluminum composite ceramic waste grinding material powder comprises the following components: zrO (ZrO) 2 :65-75wt% corundum phase Al 2 O 3 ：23-31wt％、SiO 2 :0.5-1.5wt%, fe and organic impurities: 0-4wt%.
Preferably, the dispersant is Rogowski 9300.
Preferably, the composition comprises the following components in parts by weight: 62-78 parts of low-grade tailing zircon sand, 18-28 parts of treated zirconium-aluminum composite ceramic waste grinding material powder, 2-8 parts of bauxite, 3-7 parts of dolomite, 1-2 parts of barium carbonate, 2-5 parts of yttrium oxide, 2-5 parts of sodium montmorillonite and 1-2 parts of dispersing agent.
Preferably, the composition comprises the following components in parts by weight: 65-75 parts of low-grade tailing zircon sand, 20-25 parts of treated zirconium-aluminum composite ceramic waste grinding material powder, 3-7 parts of bauxite, 4-6 parts of dolomite, 1-2 parts of barium carbonate, 2-5 parts of yttrium oxide, 2-5 parts of sodium montmorillonite and 1-2 parts of dispersing agent.
The invention also provides a preparation method of the high-strength zirconium silicate composite ceramic grinding medium, which comprises the following steps:
s1, pulverizing:
s1.1, adding water into zirconium-aluminum composite ceramic grinding waste material, pulping and filtering to obtain slurry for filtering out large-particle impurities; will beRemoving iron from slurry for filtering out large-particle impurities, and grinding to D 50 And then flash drying to obtain treated zirconium-aluminum composite ceramic waste grinding material powder with the grain size less than or equal to 0.6 mu m;
The zirconium aluminum composite ceramic grinding waste material can be waste materials generated in the grinding process of zirconium aluminum composite ceramic in the prior art; the waste materials of the zirconium oxide ceramic grinding waste material and the aluminum oxide ceramic grinding waste material can also be selected, and the components of the treated zirconium aluminum composite ceramic waste grinding material powder obtained after treatment are the same as those disclosed by the invention. Specifically, the zirconium aluminum composite ceramic grinding waste can be waste generated in the grinding process of the zirconium aluminum composite ceramic structural part produced by the eastern zirconium industry.
S1.2, adding deionized water into a ball mill, firstly adding low-grade tailing zircon sand weighed according to the proportion, sequentially adding bauxite, dolomite, barium carbonate, yttrium oxide and sodium montmorillonite weighed according to the proportion after grinding, and grinding to D, wherein the dispersant accounts for 65-75wt% of the total amount of the dispersant weighed according to the proportion 50 Less than or equal to 3 mu m, and then is transferred to a sand mill to be ground to D 50 Less than or equal to 0.4 mu m to obtain mixed slurry;
s1.3, weighing the treated zirconium-aluminum composite ceramic waste grinding material powder obtained in the step S1.1 according to a proportion, adding the powder into the mixed slurry obtained in the step S1.2, adding the rest of dispersing agent into a ball mill, mixing and grinding, and flash drying to obtain mixed powder;
S2, manufacturing a ball blank:
s2.1, preparing a molding formula glue solution, heating the molding formula glue solution to 60 ℃ and stirring for 120min for later use;
s2.2, mixing the mixed powder obtained in the step S1.3 with the glue solution of the molding formula by a mud mixer to form wetting particles; the mass ratio of the mixed powder to the aqueous solution of the molding formula glue is 90:10;
s2.3, loading the wet particles into a mould, pressing the wet particles into blocks, and crushing the blocks by using a pair of roller mill and/or a steel mill to obtain crushed particles; the crushed particles are screened by a 200-mesh screen, and fine particles below the screen are reserved for standby;
s2.4, weighing fine particles, adding the fine particles into a ball rolling machine, and then driving the particles to roll and extrude each other under the rotation of the ball rolling machine to obtain a blank; then adding water uniformly and adding the mixed powder obtained in the step S1.3; after the blank grows to the target size, wetting moisture to obtain a ball blank; taking out the obtained ball blank, naturally airing until the water content is less than or equal to 3%, and obtaining a grinding green compact;
s3, calcining:
calcining the grinding medium green body obtained in the step S2.4 in a calciner to obtain a crude grinding medium;
s4, polishing:
polishing the crude grinding medium into a finished grinding medium with a smooth surface to obtain the high-strength zirconium silicate composite ceramic grinding medium.
Preferably, in step S2.1, the aqueous solution of the molding formulation glue includes the following components in parts by weight: 2 parts of fatty alcohol alkyl sodium sulfonate, 10 parts of 10wt% maltodextrin aqueous solution and 100 parts of deionized water.
Preferably, in step S2.1, the aqueous solution of the molding formulation glue includes the following components in parts by weight: 2 parts of fatty alcohol alkyl sodium sulfonate, 5 parts of 30wt% acrylic resin aqueous solution and 100 parts of deionized water.
Preferably, in the step S3, the calcining process is as follows: heating for 8h, uniformly heating to 500 ℃ from room temperature, and preserving heat for 1h at 500 ℃; uniformly heating from 500 ℃ to 1200 ℃ for 15h, and preserving heat at 1200 ℃ for 1h; heating uniformly from 1200 ℃ to 1330 ℃ for 5 hours, and preserving heat for 2 hours at 1330 ℃; cooling to 850 ℃ for 4 hours, and carrying out heat preservation and heat treatment for 15 hours at 850 ℃; naturally cooling from 850 ℃ to room temperature.
Specifically, the preparation method of the high-strength zirconium silicate composite ceramic grinding medium comprises the following steps:
s1, pulverizing:
s1.1, adding water into the zirconium-aluminum composite ceramic grinding waste material for pulping to obtain slurry with the solid content of 50 wt%; filtering and screening the slurry by adopting a vibrating screen with the mesh number of 200 meshes to obtain slurry for filtering out large-particle impurities; the slurry filtered with large-particle impurities is ground to D after three times of iron removal by adopting an electromagnetic iron remover 50 And then flash drying to obtain treated zirconium-aluminum composite ceramic waste grinding material powder with the grain size less than or equal to 0.6 mu m;
s1.2, adding deionized water into ball millingIn the machine, firstly, the low-grade tailing zircon sand weighed according to the proportion is put into the machine, after grinding for 2 hours, bauxite, dolomite, barium carbonate, yttrium oxide and sodium montmorillonite weighed according to the proportion are put into the machine in turn, and the dispersant accounting for 65-75wt% of the total amount of the dispersant weighed according to the proportion is ground to D 50 Less than or equal to 3 mu m, and then is transferred to a sand mill to be ground to D 50 Less than or equal to 0.4 mu m to obtain mixed slurry with the solid content of 50 weight percent;
s1.3, weighing the treated zirconium-aluminum composite ceramic waste grinding material powder obtained in the step S1.1 according to a proportion, adding the powder into the mixed slurry obtained in the step S1.2, adding the rest of dispersing agent into a ball mill, mixing and grinding for 30min, and flash drying to obtain mixed powder.
S2, manufacturing a ball blank:
s2.1, preparing a molding formula glue solution, heating the molding formula glue solution to 60 ℃ and stirring for 120min for later use;
the molding formula glue solution comprises the following components in parts by weight: 2 parts of fatty alcohol sodium alkyl sulfonate (RSAS 80), 10 parts of 10wt% maltodextrin aqueous solution and 100 parts of deionized water;
or the aqueous solution of the molding formula glue comprises the following components in parts by weight: 2 parts of fatty alcohol sodium alkyl sulfonate (RSAS 80), 5 parts of 30wt% acrylic resin aqueous solution and 100 parts of deionized water;
s2.2, mixing the mixed powder obtained in the step S1 with a molding formula glue solution by a mud mixer to form wetting particles, wherein the mass ratio of the mixed powder to the molding formula glue solution is 90:10;
s2.3, the wet particles are filled into a steel mould, the wet particles are pressed into blocks by adopting the pressure of 50MPa, and the blocks are crushed by using a pair roller mill and/or a steel mill to obtain crushed particles; the crushed particles are filtered through a nylon mesh screen with 200 meshes, and fine particles below the screen are reserved for standby;
S2.4, weighing 50kg of fine particles (original spherical cores of the formed green body), adding the fine particles into a ball rolling machine, driving the particles to roll and extrude each other under the rotation of the ball rolling machine, obtaining a green body after the fine particles roll and are firm after 2 hours, then uniformly adding water at a fixed speed, adding the mixed powder obtained in the step S1.3, growing the green body layer by layer until the target size, and then tightening the wet green body for 30 minutes to obtain a spherical blank; and naturally airing the obtained ball blank after the ball blank is discharged from the machine until the water content is less than or equal to 3%, and obtaining the grinding green compact.
Specifically, during the rolling forming operation, the person skilled in the art can adjust the amount of the water and the mixed powder according to the actual forming target size, and will not be described in detail herein.
S3, calcining:
placing the grinding green compact obtained in the step S2 into a calciner, heating for 8 hours, uniformly heating to 500 ℃ from room temperature, and preserving heat for 1 hour at 500 ℃; uniformly heating from 500 ℃ to 1200 ℃ for 15h, and preserving heat at 1200 ℃ for 1h; heating uniformly from 1200 ℃ to 1330 ℃ for 5 hours, and preserving heat for 2 hours at 1330 ℃; cooling to 850 ℃ for 4 hours, and carrying out heat preservation and heat treatment for 15 hours at 850 ℃; naturally cooling the mixture from 850 ℃ to room temperature to obtain a crude grinding medium. In the process, part of amorphous crystallization is performed, meanwhile, sintering defects are passivated, and the strength of the sintered body is effectively improved.
S4, polishing:
and polishing the crude grinding medium into a finished grinding medium with a smooth surface by adopting a ball mill, a corundum abrasive and a polishing agent to obtain the high-strength zirconium silicate composite ceramic grinding medium.
The high-strength zirconium silicate composite ceramic grinding medium obtained by the invention also belongs to one of zirconium silicate beads.
The grinding medium performance of the high-strength zirconium silicate composite ceramic of the invention reaches: density of 4.25-4.28g/cm 3 (zirconium silicate beads are commercially available at present in an amount of substantially 3.8 to 4.1g/cm 3 ) The method comprises the steps of carrying out a first treatment on the surface of the Compressive strength is more than or equal to 153N
Is superior to most commercial products, more than or equal to 130N->
The abrasion of the titanium dioxide strip material is less than or equal to 27ppm/h (which is superior to most commercial products which are less than or equal to 80 ppm/h).
The invention has the action principle that:
low grade tailing zircon sand (ZrO) 2 Content of less than 60 wt.%), silicon-zirconium serious ratio deviates from zirconium silicate ZrO 2 .SiO 2 (ZrO 2 ：67.3wt％、SiO 2 :32.7 wt%) of chemical formula composition mainly consisting of zirconium silicate (about 90 wt%) and free quartz (about 10 wt%) which are wrapped in the main crystal phase zirconium silicate in a very complex combination mode, and conventional mineral separation can not be separated at all; if the mineral source is not adopted for producing the ceramic grinding medium with zirconium silicate as a main crystal phase by adopting the corresponding formula design and process treatment scheme, a large amount of glass phases are also existed in the material components besides the main crystal phase of the zirconium silicate, so that the strength and toughness of the material are obviously lower than those of the conventional zirconium silicate ceramic; therefore, how to produce high-performance zirconium silicate beads using low-grade ore sand becomes an important issue when high-quality ore sources are in the face of exhaustion. In the invention, low-grade tailing zircon sand is creatively and successfully used for producing the high-strength zirconium silicate composite ceramic grinding medium in the proportioning process.
In the prior art, the research on the forming bonding strength from the deep angles of organic-inorganic combination compound additive system, wetting speed of the additive system and powder surface and the like is rarely carried out, so that the problems of layering in rolling forming and low bonding strength are solved. The invention creatively applies the fatty alcohol alkyl sodium sulfonate, maltodextrin and acrylic resin to the ball blank forming process.
First, the present invention adopts ZrO 2 The low-grade tailing zircon sand with the content of 57-60wt% is taken as a main raw material, and the cost is far lower than that of ZrO 2 High quality zircon sand (currently spread about 8000 yuan/ton) at 66 wt%. Specifically, the Oriental zirconium ore selection field ZrO can be selected 2 The zircon sand of the low-grade tailings with the content of 57-60wt% is taken as a main raw material. Because of high impurity content, the low-grade tailing zircon sand has free quartz and TiO 2 The equivalent content is far higher than that of high-quality zircon sand, and the sintered material of the zircon sand has more glass phases, so that the strength and toughness of the grinding medium are greatly reduced, and the inventor starts from the following steps:
(1) The alumina is replaced by bauxite with lower cost and rich sources in the proportioning components, so that the bauxite is combined with free silicon oxide in the material components to generate mullite, the generation of a glass phase is reduced, the strength of the material is improved, and the influence of the free silicon on the strength is greatly solved.
(2) The method is characterized in that a zirconium-aluminum composite ceramic waste grinding material (hereinafter referred to as waste grinding material) is introduced into a formula system and used as a dispersion-enhanced framework material to carry out proper grading with a zirconium silicate main crystal phase, the annual output waste grinding material in the market should exceed 1000 tons, the waste grinding material is mainly used for carrying out iron, diamond, organic and other impurities except the zirconium and aluminum of the main crystal phase, most of iron impurities are separated through strong magnetic iron removal energy, a part of diamond can be separated through physical sieving, and the rest of diamond and the organic phase are ground into ultrafine particles to enter a matrix, so that the ultrafine particles are basically removed in the calcination and glue discharge process. The waste grinding material is obtained by grinding and crushing zirconium-aluminum composite ceramic, and the zirconium-aluminum composite ceramic main material (the main components of the main materials are zirconium oxide and aluminum oxide) has very high strength and toughness (the bending strength can reach more than 800MPa and is far higher than about 250MPa of zirconium silicate ceramic), has very good compatibility with zirconium silicate, and can be used as aggregate to be dispersed into a zirconium silicate ceramic matrix to disperse and strengthen the zirconium silicate ceramic matrix while supplementing the zirconium content, so that the influence of a small amount of residual glass phase is reduced, and the strength and toughness of the zirconium silicate matrix are greatly improved, thereby improving the compressive strength and wear resistance of products; meanwhile, the method changes waste into valuable, realizes full green recycling of zirconium resources, and completely accords with low-carbon environment-friendly production. Specifically, the waste grinding material can be selected from waste materials generated in grinding of zirconium-aluminum composite ceramic structural parts produced by the eastern zirconium industry, and the annual output of the waste grinding material is about 150 tons in the eastern zirconium industry. The waste grinding material of the zirconium-aluminum composite ceramic can be waste materials generated in grinding of zirconium-aluminum composite ceramics common in the prior art, and the components of the waste grinding material after treatment are in accordance with the components of the treated zirconium-aluminum composite ceramic waste grinding material powder described in the invention. Specifically, the components of the zirconium aluminum composite ceramic can be: 68-76wt% of zirconia and 24-32wt% of alumina.
The zirconium aluminum composite ceramic waste grinding material is different from other patents, such as those mentioned in the patent application No. 201210271942.4 of the invention, namely, low-temperature sintered zirconium silicate grinding balls and preparation methods, in that commercial zirconium oxide is directly added into the formula, and the difference is that: the sintering temperature of the commercial zirconia-based composite ceramic is generally higher than 1450 ℃, and zirconium silicate ceramic is decomposed at 1370 ℃ or higher, so that liquid phase sintering at lower than 1350 ℃ is basically adopted, the introduction of zirconia powder is sintered at about 1300 ℃ along with a ceramic matrix, a good self-sintering state is difficult to achieve, the proper strength peak value is difficult to achieve, the composite reinforcing effect is greatly reduced, and the waste grinding material used by the invention is obtained by crushing waste after the zirconia composite ceramic is sintered at 1500 ℃ and has good sintering, and the strength and toughness are high; and the cost of the commercial zirconia is tens of times that of the grinding waste.
(3) By adopting a unique sintering aid system, the sintering range can be widened and the porosity of the finished ceramic can be reduced by introducing barium carbonate into the zirconium silicate formula.
(4) Because zirconium silicate beads (with the size of 0.2mm-20 mm) are very huge in market, the technologies such as isostatic compaction, instilling and the like cannot be adapted to market demands at all due to the fact that the productivity is too small and the cost is too high, most of the zirconium silicate beads sold in the market adopt a rolling ball machine (similar to a pill forming technology of a pharmaceutical factory), such as the invention patent of low-temperature sintering zirconium silicate grinding ball and preparation method of application number 201210271942.4, the invention patent of low-temperature sintering zirconium silicate grinding medium and preparation method of application number 201310437286.5, and the invention patent of wear-resistant zirconium silicate medium ball of application number 201310706742.1 refer to the rolling ball machine; in the rolling forming process, the ball blank is mutually rolled and extruded under the wetting action of the formula water by the repeated circulation of water spraying, rolling, powder adding and rolling, and the powder is adhered to the blank cores layer by layer to gradually grow up to form a target ball blank. The mode of combining the intermittent ball blank and the dry powder has extremely high requirements on the bonding force between powder layers, the defects of poor density, layering, cracks and the like of the ball blank often exist, layering is gradually serious along with the growth of the ball blank (more than or equal to 3 mm), and the mode is one of main reasons for low strength of the roll-formed ceramic grinding ball, so that the commercial zirconium silicate bead is difficult to have the roll-formed zirconium silicate bead with the thickness of more than 3mm, and the use of the process is greatly limited. In the industry, adhesives such as PVA, CMC and the like are simply added into the rolling forming formula water to improve the forming performance, but Because the bonding time is very short (within a few seconds) in the production process, the organic components are difficult to sufficiently wet the powder surface to achieve interlayer firm bonding, and delamination is sometimes accelerated, so that the effect is not ideal. In order to solve the problem, the inventor adopts an original organic penetrating agent sodium fatty alcohol alkyl sulfonate (RSAS 80) to compound maltodextrin or acrylic resin in a molding system, and combines an inorganic bonding agent sodium montmorillonite composite system; the osmotic agent fatty alcohol alkyl sodium sulfonate (RSAS 80) can quickly reduce the surface tension of an organic binder system in a short time, so that the organic binder system can quickly permeate to the inner surface of the porous powder in a few seconds, and is fully combined with the powder through the actions of adsorption, electrostatic attraction or bonding, so that the wettability speed and the bonding strength of a glue system (maltodextrin or acrylic resin) and the powder are greatly enhanced, and interlayer layering is effectively avoided. Sodium montmorillonite is layered aluminosilicate mineral with water molecules and exchangeable cations between layers, and large radius cations such as K are adsorbed between the layers + 、Na + 、Ca 2+ 、Mg 2+ 、Li + 、H + Etc., these cations are present in a hydrated state; the special structure causes that the montmorillonite has very strong adsorptivity, after absorbing water or absorbing organic substances, the spacing between crystal layers is rapidly increased, the volume expansion multiple is up to 20-30 times, and the plasticity is very good. By utilizing the comprehensive characteristics, after the sodium montmorillonite and other components (other components except the sodium montmorillonite) in the mixed powder are fully mixed and adsorbed, the mixed mud material has excellent plasticity, the mud cake detection plasticity can reach more than 80 percent, and the mud material is greatly higher than the mud material system plasticity when the sodium montmorillonite is not added, and meanwhile, the mud material system has extremely high adsorptivity and self-adhesion. The powder can be sprayed, rolled, extruded and adhered to the billet core layer by layer in the rolling process of spraying water, rolling, adding powder, rolling, extruding, greatly improving the wetting adhesion between the powder and an organic compound system (maltodextrin or acrylic resin), finally achieving the mutual adsorption between the powder layers, and achieving the mutual extrusion embedding between the layers through extremely high plasticity, thereby improving the bonding strength between the layers and effectively improving the bonding strength of the ball billet. The active ingredients of the silicon, aluminum and bauxite are finally in a sintered body The mullite network structure is formed to have a certain improvement effect on the strength and toughness of the material. The organic-inorganic combined compound reinforcing system greatly improves the bonding strength between layers, effectively inhibits layering in the forming process and improves the strength of the grinding medium green body.
(5) In the sintering process, a sintering curve is designed, normal pressure liquid phase sintering is combined with medium temperature amorphous phase crystallization treatment to improve the strength of the porcelain body, and microscopic defects are passivated. The material has a high-toughness framework structure combined with a finer matrix grain structure, and has high toughness, wear resistance, flushing resistance and corrosion resistance; finally, the high-strength zirconium silicate composite ceramic grinding medium is subjected to fine polishing processing to obtain wear resistance, and the wear is superior to that of the conventional zirconium silicate beads; the service life is longer than that of the conventional zirconium silicate beads, and the cost is greatly reduced.
Compared with the prior art, the invention has the beneficial effects that:
the raw material cost is low, the preparation method is simple, the prepared high-strength zirconium silicate composite ceramic grinding medium has high strength, high toughness, high wear resistance, high flushing resistance, high corrosion resistance and high wear resistance, and the abrasion is superior to that of the conventional zirconium silicate beads; the service life is longer than that of the conventional zirconium silicate beads, the cost is greatly reduced compared with that of the conventional zirconium silicate beads, and a green regeneration way is provided for the zirconium-aluminum composite ceramic waste grinding material.
In the preparation process, the low-grade tailing zircon sand is adopted as a main raw material, so that the processing cost is greatly reduced; the treated zirconium-aluminum composite ceramic waste grinding material powder prepared by introducing the zirconium-aluminum composite ceramic waste grinding material into a formula system greatly improves the strength and toughness of a zirconium silicate matrix, thereby improving the compressive strength and wear resistance of the product; meanwhile, the waste is changed into valuable, the full green recycling of zirconium resources is realized, and the method completely accords with low-carbon environment-friendly production; in the preparation method, the organic penetrating agent fatty alcohol sodium alkyl sulfonate (RSAS 80) is creatively used for compounding maltodextrin or acrylic resin, and an inorganic binding agent sodium montmorillonite composite system is combined, so that the bonding strength between layers is greatly improved, layering in the forming process is effectively inhibited, and the strength of the grinding green compact is improved.
Drawings
FIG. 1 shows the result of example 1 of the present invention
A picture of a high-strength zirconium silicate composite ceramic grinding medium;
FIG. 2 is a photograph of the zirconium aluminum composite ceramic grinding waste of the present invention;
FIG. 3 is a photograph of the treated zirconium aluminum composite ceramic waste grinding material powder of the present invention;
FIG. 4 shows the result of example 1 of the present invention
SEM images of the high strength zirconium silicate composite ceramic grinding medium;
FIG. 5 is a schematic diagram of a commercial product
SEM images of zirconium silicate beads;
FIG. 6 shows the result of example 1 of the present invention
XRD pattern of the high strength zirconium silicate composite ceramic grinding medium;
FIG. 7 is a diagram of the embodiment 1 of the present invention
A cross-sectional view of a high strength zirconium silicate composite ceramic grinding medium;
FIG. 8 is a schematic diagram of a conventional bonding process
A cross-sectional view of a zirconium silicate ceramic grinding medium;
FIG. 9 is a diagram of the embodiment 1 of the present invention
Back-scattered electron patterns of the high strength zirconium silicate composite ceramic grinding medium.
Detailed Description
The invention is further described in terms of specific examples, illustrative examples and illustrations of which are provided herein to illustrate the invention, but are not to be construed as limiting the invention.
Example 1
The high-strength zirconium silicate composite ceramic grinding medium comprises the following components in parts by weight: 70 parts of low-grade tailing zircon sand, 23 parts of treated zirconium-aluminum composite ceramic waste grinding material powder, 5 parts of bauxite, 5 parts of dolomite, 1.5 parts of barium carbonate, 3.5 parts of yttrium oxide, 3.5 parts of sodium montmorillonite and 1.5 parts of dispersing agent.
ZrO in the low-grade tailing zircon sand 2 The content of (2) was 58.5wt%; specifically adopts low-grade tailing zircon sand of Oriental zirconium ore dressing sites.
The treated zirconium-aluminum composite ceramic waste grinding material powder comprises the following components: zrO (ZrO) 2 :70wt% corundum phase Al 2 O 3 ：27wt％、SiO 2 :1wt%, fe and organic impurities: 2wt%. The dispersing agent is Robin Hasi 9300.
The preparation method of the high-strength zirconium silicate composite ceramic grinding medium comprises the following steps:
s1, pulverizing:
s1.1, adding water into the zirconium-aluminum composite ceramic grinding waste material for pulping to obtain slurry with the solid content of 50 wt%; filtering and screening the slurry by adopting a vibrating screen with the mesh number of 200 meshes to obtain slurry for filtering out large-particle impurities; the slurry filtered with large-particle impurities is ground to D after three times of iron removal by adopting an electromagnetic iron remover 50 And then flash drying to obtain treated zirconium-aluminum composite ceramic waste grinding material powder with the grain size less than or equal to 0.6 mu m; the zirconium-aluminum composite ceramic grinding waste is waste generated in the grinding process of zirconium-aluminum composite ceramic structural parts produced by the eastern zirconium industry.
S1.2, adding deionized water into a ball mill, firstly adding low-grade tailing zircon sand weighed according to the proportion, grinding for 2 hours, sequentially adding bauxite, dolomite, barium carbonate, yttrium oxide and sodium montmorillonite weighed according to the proportion, adding a dispersing agent accounting for 65-75wt% of the total amount of the dispersing agent weighed according to the proportion, and grinding to D 50 Less than or equal to 3 mu m, and then is transferred to a sand mill to be ground to D 50 Less than or equal to 0.4 mu m to obtain mixed slurry with the solid content of 50 weight percent;
S1.3, weighing the treated zirconium-aluminum composite ceramic waste grinding material powder obtained in the step S1.1 according to a proportion, adding the powder into the mixed slurry obtained in the step S1.2, adding the rest of dispersing agent into a ball mill, mixing and grinding for 30min, and flash drying to obtain mixed powder.
S2, manufacturing a ball blank:
s2.1, preparing a molding formula glue solution, heating the molding formula glue solution to 60 ℃ and stirring for 120min for later use;
the molding formula glue solution comprises the following components in parts by weight: 2 parts of fatty alcohol sodium alkyl sulfonate (RSAS 80), 10 parts of 10wt% maltodextrin aqueous solution and 100 parts of deionized water;
s2.2, mixing the mixed powder obtained in the step S1 with a molding formula glue solution by a mud mixer to form wetting particles, wherein the mass ratio of the mixed powder to the molding formula glue solution is 90:10;
s2.3, the wet particles are filled into a steel mould, the wet particles are pressed into blocks by adopting the pressure of 50MPa, and the blocks are crushed by using a pair roller mill and/or a steel mill to obtain crushed particles; the crushed particles are filtered through a nylon mesh screen with 200 meshes, and fine particles below the screen are reserved for standby;
s2.4, weighing 50kg of fine particles (original spherical cores of the formed green body), adding the fine particles into a ball rolling machine, driving the particles to roll and extrude each other under the rotation of the ball rolling machine, obtaining a green body after the fine particles roll and are firm after 2 hours, then uniformly adding water at a fixed speed, adding the mixed powder obtained in the step S1.3, growing the green body layer by layer until the target size, and then tightening the wet green body for 30 minutes to obtain a spherical blank; and naturally airing the obtained ball blank after the ball blank is discharged from the machine until the water content is less than or equal to 3%, and obtaining the grinding green compact.
S3, calcining:
placing the grinding green compact obtained in the step S2 into a calciner, heating for 8 hours, uniformly heating to 500 ℃ from room temperature, and preserving heat for 1 hour at 500 ℃; uniformly heating from 500 ℃ to 1200 ℃ for 15h, and preserving heat at 1200 ℃ for 1h; heating uniformly from 1200 ℃ to 1330 ℃ for 5 hours, and preserving heat for 2 hours at 1330 ℃; cooling to 850 ℃ for 4 hours, and carrying out heat preservation and heat treatment for 15 hours at 850 ℃; naturally cooling the mixture from 850 ℃ to room temperature to obtain a crude grinding medium.
S4, polishing:
and polishing the crude grinding medium into a finished grinding medium with a smooth surface by adopting a ball mill, a corundum abrasive and a polishing agent to obtain the high-strength zirconium silicate composite ceramic grinding medium.
According to the proportion and the preparation method of the example 1, the preparation
High-strength zirconium silicate composite ceramic grinding medium, < >>
High-strength zirconium silicate composite ceramic grinding medium, < >>
Grinding medium green body of high-strength zirconium silicate composite ceramic grinding medium, < >>
High-strength zirconium silicate composite ceramic grinding medium and +.>
High-strength zirconium silicate composite ceramic grinding medium.
Comparative example 1
The conventional bonding process was carried out in the same proportion as in example 1, and the preparation method was the same as in example 1 except for steps S2.1 and S2.2.
The steps S2.1 and S2.2 of the conventional bonding process preparation method are specifically as follows:
S2.1, preparing an adhesive, wherein the adhesive is a PVA aqueous solution with the mass fraction of 7 wt%;
s2.2, mixing the mixed powder obtained in the step S1 with an adhesive to form wetting particles by adopting a mud mixer, wherein the mass ratio of the mixed powder to the adhesive is 90:10.
according to the proportion and the preparation method of the comparative example 1, the conventional bonding process is obtainedIs prepared to obtain
Zirconium silicate ceramic grinding medium prepared by conventional bonding process>
Grinding medium green body of zirconium silicate ceramic grinding medium and prepared by conventional bonding process>
Zirconium silicate ceramic grinding medium.
As shown in FIG. 1, the method of example 1 of the present invention is
A picture of a high strength zirconium silicate composite ceramic grinding medium.
FIG. 2 is a photograph of the zirconium aluminum composite ceramic grinding waste of the present invention; as shown in FIG. 3, the image of the zirconium aluminum composite ceramic waste grinding material powder treated by the method is shown. The figure shows that the zirconium-aluminum composite ceramic grinding waste has more impurities and caking phenomenon, and the treated zirconium-aluminum composite ceramic waste grinding material powder meets the use requirement after being treated.
As shown in FIG. 4, the method of example 1 of the present invention is
SEM images of the high strength zirconium silicate composite ceramic grinding medium. As shown in FIG. 5, commercially available +. >
SEM images of zirconium silicate beads. Here, commercially available->
Zirconium silicate beads of Suzhou Union New ceramic materials Co., ltd +.>
Zirconium silicate beads of (2)./>
From the SEM image, commercially available products can be seen
The zirconium silicate bead does not carry out formula design on the free quartz and adds a large amount of sintering aids to lead the matrix to contain a large amount of glass phases, but the high-strength zirconium silicate composite ceramic grinding medium of the invention sinters the free quartz and high-quality bauxite to generate network structure mullite through formula design, thereby greatly improving the mechanical property of the matrix; meanwhile, the glass phase is effectively reduced by assisting an effective heat treatment process.
As shown in FIG. 6, the method of example 1 of the present invention
XRD pattern of the high strength zirconium silicate composite ceramic grinding medium.
As shown in FIG. 7, the method of example 1 of the present invention
A cross-sectional view of the high-strength zirconium silicate composite ceramic grinding medium. As shown in FIG. 8, the +.A.prepared by the conventional bonding process>
A cross-sectional view of a zirconium silicate ceramic grinding medium. Prepared by conventional bonding process>
The zirconium silicate ceramic grinding medium has weaker bonding force between layers, and the section is layered. The +.1 of the invention>
The bonding force between layers of the high-strength zirconium silicate composite ceramic grinding medium is enhanced, and the section is perfect.
As shown in FIG. 9, the method of example 1 of the present invention
Back-scattered electron patterns of the high strength zirconium silicate composite ceramic grinding medium. From this figure, it can be seen that the zirconia in the treated zirconium-aluminum composite ceramic waste grinding stock powder is dispersed in the high strength zirconium silicate composite ceramic grinding medium matrix.
Randomly selecting 10 pieces prepared by conventional bonding process
10 grinding media green bodies of zirconium silicate ceramic grinding media obtained in example 1 of the invention>
The green grinding media of the high-strength zirconium silicate composite ceramic grinding media are compared in compressive strength, and the comparison results are shown in table 1:
TABLE 1
As can be seen from Table 1, the composition obtained in example 1 of the present invention
The strength of the grinding medium green body of the high-strength zirconium silicate composite ceramic grinding medium is improved by 30 percent.
Randomly selecting 10 pieces prepared by conventional bonding process
10 zirconium silicate ceramic grinding media of the invention obtained in example 1 +.>
The compressive strength, abrasion and density of the high-strength zirconium silicate composite ceramic grinding medium are compared, and the comparison result is shown in table 2:
TABLE 2
From the data in the table, the data obtained in example 1 of the present invention can be derived
The compressive strength of the high-strength zirconium silicate composite ceramic grinding medium is improved by 24.5%, the density is improved by 2%, and the abrasion is reduced by 37.5%.
From the data in tables 1 and 2, it can be seen that the compressive strength of the green grinding media of the high-strength zirconium silicate composite ceramic grinding media obtained in example 1 is higher than that of the green grinding media of the zirconium silicate ceramic grinding media prepared by the conventional bonding process. Furthermore, the compressive strength and density of the high-strength zirconium silicate composite ceramic grinding medium obtained in the embodiment 1 are higher than those of the zirconium silicate ceramic grinding medium prepared by the conventional bonding process; and the abrasion of the high-strength zirconium silicate composite ceramic grinding medium obtained in the example 1 is lower than that of the zirconium silicate ceramic grinding medium prepared by a conventional bonding process. Therefore, the organic penetrating agent fatty alcohol sodium alkyl sulfonate (RSAS 80) used in the invention is compounded with maltodextrin, and is combined with an inorganic binding agent sodium montmorillonite composite system, so that the bonding strength between layers is greatly improved, layering in the forming process is effectively inhibited, and the strength of the grinding medium green compact is improved.
The product obtained in example 1
High strength zirconium silicate composite ceramic grinding medium and commercial product
Zirconium silicate beads were compared and the comparison results are shown in table 3. Here, commercially available ∈ ->
Zirconium silicate beads were prepared from Suzhou Union ceramic materials Co., ltd ++ >
Zirconium silicate beads of (2).
TABLE 3 Table 3
10 batches of the same size product were prepared according to the formulation of example 1 and steps S1 to S2 in the preparation method
Then, each batch was equally divided into four groups, and the conditions of "time for heat treatment at 850 ℃ in step S3" were changed, and a comparative test was performed, and the other steps and ratios were the same as those in example 1, and the data of table 4 were obtained:
TABLE 4 Table 4
From the data in the table, the content of the glass phase is reduced by the medium and low temperature for a long time, the strength of the high-strength zirconium silicate composite ceramic grinding medium is improved by about 8%, and the wear resistance is also improved.
Example 2
The high-strength zirconium silicate composite ceramic grinding medium comprises the following components in parts by weight: 75 parts of low-grade tailing zircon sand, 20 parts of treated zirconium-aluminum composite ceramic waste grinding material powder, 7 parts of bauxite, 4 parts of dolomite, 2 parts of barium carbonate, 2 parts of yttrium oxide, 5 parts of sodium montmorillonite and 1 part of dispersing agent.
ZrO in the low-grade tailing zircon sand 2 The content of (2) was 58.5wt%; specifically adopts low-grade tailing zircon sand of Oriental zirconium ore dressing sites.
The treated zirconium-aluminum composite ceramic waste grinding material powder comprises the following components: zrO (ZrO) 2 :70wt% corundum phase Al 2 O 3 ：27wt％、SiO 2 :1wt%, fe and organic impurities: 2wt%.
The dispersing agent is Robin Hasi 9300.
The preparation method of the high-strength zirconium silicate composite ceramic grinding medium is the same as that of the example 1.
Example 3
The high-strength zirconium silicate composite ceramic grinding medium comprises the following components in parts by weight: 65 parts of low-grade tailing zircon sand, 25 parts of treated zirconium-aluminum composite ceramic waste grinding material powder, 3 parts of bauxite, 6 parts of dolomite, 1 part of barium carbonate, 5 parts of yttrium oxide, 2 parts of sodium montmorillonite and 2 parts of dispersing agent.
ZrO in the low-grade tailing zircon sand 2 The content of (2) was 58.5wt%; specifically adopts low-grade tailing zircon sand of Oriental zirconium ore dressing sites.
The treated zirconium-aluminum composite ceramic waste grinding material powder comprises the following components: zrO (ZrO) 2 :70wt% corundum phase Al 2 O 3 ：27wt％、SiO 2 :1wt%, fe and organic impurities: 2wt%.
The dispersing agent is Robin Hasi 9300.
The preparation method of the high-strength zirconium silicate composite ceramic grinding medium is the same as that of the example 1.
Example 4
The high-strength zirconium silicate composite ceramic grinding medium comprises the following components in parts by weight: 62 parts of low-grade tailing zircon sand, 28 parts of treated zirconium-aluminum composite ceramic waste grinding material powder, 2 parts of bauxite, 7 parts of dolomite, 1 part of barium carbonate, 5 parts of yttrium oxide, 2 parts of sodium montmorillonite and 2 parts of dispersing agent.
ZrO in the low-grade tailing zircon sand 2 The content of (2) was 60% by weight. Specifically adopts low-grade tailing zircon sand of Oriental zirconium ore dressing sites.
The treated zirconium-aluminum composite ceramic waste grinding material powder comprises the following components: zrO (ZrO) 2 :65wt% corundum phase Al 2 O 3 ：31wt％、SiO 2 :1.5wt%, fe and organic impurities: 2.5wt%. The dispersing agent is Robin Hasi 9300.
The preparation method of the high-strength zirconium silicate composite ceramic grinding medium comprises the following components in parts by weight: 2 parts of fatty alcohol sodium alkyl sulfonate (RSAS 80), 5 parts of 30wt% acrylic resin aqueous solution and 100 parts of deionized water; the remainder was the same as in example 1.
Example 5
The high-strength zirconium silicate composite ceramic grinding medium comprises the following components in parts by weight: 78 parts of low-grade tailing zircon sand, 18 parts of treated zirconium-aluminum composite ceramic waste grinding material powder, 8 parts of bauxite, 3 parts of dolomite, 2 parts of barium carbonate, 2 parts of yttrium oxide, 5 parts of sodium montmorillonite and 1 part of dispersing agent.
ZrO in the low-grade tailing zircon sand 2 The content of (2) was 60% by weight. Specifically adopts low-grade tailing zircon sand of Oriental zirconium ore dressing sites.
The treated zirconium-aluminum composite ceramic waste grinding material powder comprises the following components: zrO (ZrO) 2 :65wt% corundum phase Al 2 O 3 ：31wt％、SiO 2 :1.5wt%, fe and organic impurities: 2.5wt%.
The dispersing agent is Robin Hasi 9300.
The preparation method of the high-strength zirconium silicate composite ceramic grinding medium is the same as that of example 4.
Example 6
The high-strength zirconium silicate composite ceramic grinding medium comprises the following components in parts by weight: 80 parts of low-grade tailing zircon sand, 15 parts of zirconium-aluminum composite ceramic waste grinding material, 10 parts of bauxite, 2 parts of dolomite, 3 parts of barium carbonate, 2 parts of yttrium oxide, 5 parts of sodium montmorillonite and 1 part of dispersing agent.
ZrO in the low-grade tailing zircon sand 2 The content of (2) was 57wt%; specifically adopts low-grade tailing zircon sand of Oriental zirconium ore dressing sites.
The treated zirconium-aluminum composite ceramic waste grinding material powder comprises the following components: zrO (ZrO) 2 :72.5wt% corundum phase Al 2 O 3 ：23wt％、SiO 2 :0.5wt%, fe and organic impurities: 4wt%. The dispersing agent is Robin Hasi 9300.
The preparation method of the high-strength zirconium silicate composite ceramic grinding medium is the same as that of the example 1.
Example 7
The high-strength zirconium silicate composite ceramic grinding medium comprises the following components in parts by weight: 60 parts of low-grade tailing zircon sand, 30 parts of treated zirconium-aluminum composite ceramic waste grinding material powder, 1 part of bauxite, 8 parts of dolomite, 1 part of barium carbonate, 5 parts of yttrium oxide, 2 parts of sodium montmorillonite and 2 parts of dispersing agent.
ZrO in the low-grade tailing zircon sand 2 The content of (2) was 57wt%; specifically adopts low-grade tailing zircon sand of Oriental zirconium ore dressing sites.
The treated zirconium-aluminum composite ceramic waste grinding material powder comprises the following components: zrO (ZrO) 2 :72.5wt% corundum phase Al 2 O 3 ：23wt％、SiO 2 :0.5wt%, fe and organic impurities: 4wt%. The dispersing agent is Robin Hasi 9300.
The preparation method of the high-strength zirconium silicate composite ceramic grinding medium is the same as that of the example 1.
The technical scheme of the invention is not limited to the specific embodiment, and all technical modifications made according to the technical scheme of the invention fall within the protection scope of the invention.
Claims (10)
1. A high-strength zirconium silicate composite ceramic grinding medium is characterized in that: comprises the following components in parts by weight: 60-80 parts of low-grade tailing zircon sand, 15-30 parts of treated zirconium-aluminum composite ceramic waste grinding material powder, 0-10 parts of bauxite, 2-8 parts of dolomite, 1-3 parts of barium carbonate, 2-5 parts of yttrium oxide, 2-5 parts of sodium montmorillonite and 1-2 parts of dispersing agent.
2. The high strength zirconium silicate composite ceramic grinding medium of claim 1, wherein: zrO in the low-grade tailing zircon sand 2 The content of (C) is 57-60wt%.
3. The high strength zirconium silicate composite ceramic grinding medium of claim 1, wherein: the treated zirconium-aluminum composite ceramic waste The grinding material powder comprises the following components: zrO (ZrO) 2 :65-75wt% corundum phase Al 2 O 3 ：23-31wt％、SiO 2 :0.5-1.5wt%, fe and organic impurities: 0-4wt%.
4. The high strength zirconium silicate composite ceramic grinding medium of claim 1, wherein: the dispersing agent is Robin Hasi 9300.
5. The high strength zirconium silicate composite ceramic grinding medium of claim 1, wherein: comprises the following components in parts by weight: 62-78 parts of low-grade tailing zircon sand, 18-28 parts of treated zirconium-aluminum composite ceramic waste grinding material powder, 2-8 parts of bauxite, 3-7 parts of dolomite, 1-2 parts of barium carbonate, 2-5 parts of yttrium oxide, 2-5 parts of sodium montmorillonite and 1-2 parts of dispersing agent.
6. The high strength zirconium silicate composite ceramic grinding medium of claim 1, wherein: comprises the following components in parts by weight: 65-75 parts of low-grade tailing zircon sand, 20-25 parts of treated zirconium-aluminum composite ceramic waste grinding material powder, 3-7 parts of bauxite, 4-6 parts of dolomite, 1-2 parts of barium carbonate, 2-5 parts of yttrium oxide, 2-5 parts of sodium montmorillonite and 1-2 parts of dispersing agent.
7. The method for preparing the high-strength zirconium silicate composite ceramic grinding medium according to any one of claims 1 to 6, which is characterized in that: the method comprises the following steps:
S1, pulverizing:
s1.1, adding water into zirconium-aluminum composite ceramic grinding waste material, pulping and filtering to obtain slurry for filtering out large-particle impurities; removing iron from the slurry with the large-particle impurities filtered out, and grinding to D 50 And then flash drying to obtain treated zirconium-aluminum composite ceramic waste grinding material powder with the grain size less than or equal to 0.6 mu m;
s1.2, adding deionized water into a ball mill, firstly adding low-grade tailing zircon sand weighed according to the proportion, grinding, and then sequentially adding bauxite, dolomite, barium carbonate, yttrium oxide and sodium montmorillonite weighed according to the proportion, anddispersing agent accounting for 65-75wt% of the total amount of the weighed dispersing agent according to the proportion, and grinding the dispersing agent to D 50 Less than or equal to 3 mu m, and then is transferred to a sand mill to be ground to D 50 Less than or equal to 0.4 mu m to obtain mixed slurry;
s1.3, weighing the treated zirconium-aluminum composite ceramic waste grinding material powder obtained in the step S1.1 according to a proportion, adding the powder into the mixed slurry obtained in the step S1.2, adding the rest of dispersing agent into a ball mill, mixing and grinding, and flash drying to obtain mixed powder;
s2, manufacturing a ball blank:
s2.1, preparing a molding formula glue solution, heating the molding formula glue solution to 60 ℃ and stirring for 120min for later use;
s2.2, mixing the mixed powder obtained in the step S1.3 with the glue solution of the molding formula by a mud mixer to form wetting particles; the mass ratio of the mixed powder to the aqueous solution of the molding formula glue is 90:10;
S2.3, loading the wet particles into a mould, pressing the wet particles into blocks, and crushing the blocks by using a pair of roller mill and/or a steel mill to obtain crushed particles; the crushed particles are screened by a 200-mesh screen, and fine particles below the screen are reserved for standby;
s2.4, weighing fine particles, adding the fine particles into a ball rolling machine, and then driving the particles to roll and extrude each other under the rotation of the ball rolling machine to obtain a blank; then adding water uniformly and adding the mixed powder obtained in the step S1.3; after the blank grows to the target size, wetting moisture to obtain a ball blank; taking out the obtained ball blank, naturally airing until the water content is less than or equal to 3%, and obtaining a grinding green compact;
s3, calcining:
calcining the grinding medium green body obtained in the step S2.4 in a calciner to obtain a crude grinding medium;
s4, polishing:
polishing the crude grinding medium into a finished grinding medium with a smooth surface to obtain the high-strength zirconium silicate composite ceramic grinding medium.
8. The method for preparing the high-strength zirconium silicate composite ceramic grinding medium according to claim 7, which is characterized in that: in step S2.1, the aqueous solution of the molding formulation glue includes the following components in parts by weight: 2 parts of fatty alcohol alkyl sodium sulfonate, 10 parts of 10wt% maltodextrin aqueous solution and 100 parts of deionized water.
9. The method for preparing the high-strength zirconium silicate composite ceramic grinding medium according to claim 7, which is characterized in that: in step S2.1, the aqueous solution of the molding formulation glue includes the following components in parts by weight: 2 parts of fatty alcohol alkyl sodium sulfonate, 5 parts of 30wt% acrylic resin aqueous solution and 100 parts of deionized water.
10. The method for preparing the high-strength zirconium silicate composite ceramic grinding medium according to claim 7, which is characterized in that: in the step S3, the calcining process is as follows: heating for 8h, uniformly heating to 500 ℃ from room temperature, and preserving heat for 1h at 500 ℃; uniformly heating from 500 ℃ to 1200 ℃ for 15h, and preserving heat at 1200 ℃ for 1h; heating uniformly from 1200 ℃ to 1330 ℃ for 5 hours, and preserving heat for 2 hours at 1330 ℃; cooling to 850 ℃ for 4 hours, and carrying out heat preservation and heat treatment for 15 hours at 850 ℃; naturally cooling from 850 ℃ to room temperature.
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